coatings
Article
Enhanced Electrochromic Properties of Nanostructured WO3
Film by Combination of Chemical and Physical Methods
Xiaoni Li 1 , Zhijie Li 1 , Wanting He 1 , Haolin Chen 1 , Xiufeng Tang 1,2, *, Yeqing Chen 1, * and Yu Chen 3, *






Citation: Li, X.; Li, Z.; He, W.;
Chen, H.; Tang, X.; Chen, Y.; Chen, Y.
Enhanced Electrochromic Properties
of Nanostructured WO3 Film by
Combination of Chemical and
Physical Methods. Coatings 2021, 11,
959. https://doi.org/10.3390/
coatings11080959
Academic Editor: Emmanuel
Koudoumas
Received: 7 June 2021
Accepted: 7 August 2021
Published: 12 August 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
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iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Coatings 2021, 11, 959. https://doi.org/10.3390/coatings11080959
1 School of Applied Physics and Materials, Wuyi University, Jiangmen 529020, China;
nx10909168@163.com (X.L.); z598414677@outlook.com (Z.L.); oneselfhappy@foxmail.com (W.H.);
13226254599@163.com (H.C.)
2 Research Center of Flexible Sensing Materials and Devices, Wuyi University, Jiangmen 529020, China
3 Analysis and Test Center, Guangdong University of Technology, Guangzhou 511400, China
* Correspondence: xiufengtang@wyu.edu.cn (X.T.); yeqingchen@ciac.ac.cn (Y.C.);
atc_chenyu@gdut.edu.cn (Y.C.)
Abstract: WO3 films are the most widely used electrochromic functional layers. It is known that
WO3 films prepared by pure chemical method generally possess novel nanostructures, but the
adhesion between WO3 films and substrates is weak. However, WO3 films prepared by pure physical
method usually show relatively dense morphology, which limits their electrochromic properties.
In order to break through these bottlenecks and further improve their electrochromic properties,
this work first prepared nanostructured WO3 powder by chemical method, and then using this
powder as the evaporation source, nanostructured WO3 films were fabricated by vacuum thermal
evaporation method. Properties of nanostructured WO3 films were systematically compared with
those of ordinary WO3 films. It turned out that the nanostructured WO3 film exhibited better cyclic
stability and memory effect, and also the optical modulation rate was 14% higher than that of the
ordinary WO3 film. More importantly, the nanostructured WO3 film showed better adhesion with
the ITO substrates. These results demonstrate that a combination of chemical and physical methods
is an effective preparation method to improve the electrochromic properties of WO3 films.
Keywords: WO3 film; nanostructured; electrochromic; combination of chemical and physical methods
1. Introduction
Tungsten oxide (WO3 ) has been regarded as the most promising electrochromic
material due to its wide range of continuously adjustable optical properties, excellent
reversibility, low energy consumption, high coloration efficiency, and environmental friend-
liness [1–3]. WO3 films have been used in electrochromic smart windows [4,5], information
display [6], photocatalysis [7,8], and energy storage technologies [9,10]. Therefore, further
improving the properties of WO3 films has become one of the research hot spots.
As we know, the electrochemical properties of WO3 films depend strongly on their
preparation method, morphology and structure. Owing to the high surface activity and
loose morphology, nanostructured WO3 can accelerate the electrochemical process and
improve the electrochromic properties with respect to the bulk counterparts [11–14]. So
far, various nanostructured WO3 , such as nanowires [15], nanorods [16,17], nanocolumnar
films [18] and nanoparticles [19] have been prepared and shown good electrochromic
properties. Nanostructured WO3 films have been fabricated by various physical and
chemical methods, including sol-gel [20], hydrothermal [21], magnetron sputtering [22] and
electron-beam evaporation [23], which are just pure chemical or physical methods. Though
WO3 films prepared by pure chemical method generally possess novel nanostructures,
the adhesion between WO3 films and substrates is weak. On the other hand, WO3 films
prepared by pure physical method such as vacuum thermal evaporation and magnetron
sputtering have many advantages, but their morphology is relatively dense, which limits
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Coatings 2021, 11, 959 2 of 10

the electrochromic properties [24]. Therefore, WO3 films prepared by pure chemical or
physical methods lead to the property bottleneck to some extent [25].
Herein, instead of using pure chemical method or pure physical method, nanos-
tructured WO3 films were prepared by combination of chemical and physical methods.
First, nanostructured WO3 powder was prepared through chemical synthesis, and then
nanostructured WO3 films were fabricated using vacuum thermal evaporation. Their
characterization and electrochromic properties were compared with ordinary WO3 films
at the same thickness. Particularly, herein the adhesion between the WO3 film and the
substrate was discussed, which was a key factor in real application of the electrochromic
devices but was rarely present in the literature.

2. Materials and Methods

2.1. Sample Preparation
The preparation process was shown in Figure 1. The same amount of 0.025 mol
Na2 WO4 ·2H2 O and CaCl2 were respectively dissolved in 50 mL of deionized water, and
0.5 mol/L Na2 WO4 solution and CaCl2 solution were prepared. Then, the two solutions
were mixed together and HCl was added to adjust the solution pH to be neutral and
left to stand for 72 h. The precipitate was filtered and dried at 70 ◦ C to obtain CaWO4
powder. Next, CaWO4 powder was dissolved in 100 mL 20% HCl. After standing for 324ofh,
Coatings 2021, 11, x FOR PEER REVIEW 10
nanostructured WO3 powder was obtained by filtration and drying. In the end, the powder
was annealed at 500 ◦ C for 2 h.

Figure1.1.Preparation
Figure Preparationprocess
processdiagram
diagramofofnanostructured
nanostructuredWO
WO3 3powder
powderand
andfilm.
film.

The indium tin oxide (ITO) glass substrate was used and first subjected to cleaning of
2.2. Characterization
acetone, alcohol and deionized water. Then, the nanostructured WO3 film was prepared by
Morphology of two kinds of WO3 powder and two kinds of WO3 films was observed
vacuum thermal evaporation (ZHD-300N, Technol, Beijing, China) using the nanostruc-
by scanning electron microscopy (SEM) using a Sigma 500 instrument (Zeiss, Oberkochen,
tured WO3 powder as the evaporation source. The distance between substrates and the
Germany). The structure was examined by X-ray diffraction (XRD) analysis using a Cu Ka
evaporation source was 11.5 cm. Oxygen and argon were let into the vacuum chamber with
radiation (Philips X’Pert diffractometer, Amsterdam, The Netherland). X-ray photoelec-
the flow ratio of 2:3, where oxygen was introduced to avoid the WO3 vapor from being
tron spectroscopy (XPS) analysis was performed by using a Thermo Fisher Scientific ES-
depleted of oxygen during the long-time evaporation [26], ensuring the WO3 deposition
CALAB 250 XPS system, Waltham, MA, USA. The cyclic stability of WO3 film was meas-
on the substrate. The working pressure was 1.0 Pa, and the temperature of the tungsten
ured by cyclic voltammetry (CV) and the response time was tested by electrochemical
boat was kept at 1100 ◦ C for 1.5 h. At this time, the temperature of the substrate varied
double potential step chronograph current test (CA) on an electrochemical workstation
slightly in the range of 340–350 ◦ C. The substrate rotated at the speed of 10 r/min during
(CHI760E). A three-electrode system was formed using WO3 film as the working elec-
the whole process. Finally, nanostructured WO3 films were obtained at a thickness of
trode,400
about Ag/AgCl
nm. In as the reference
addition, electrode,
ordinary WO3 filmsmetal
withPt the
plate as the
same counter
thickness electrode,
were preparedandby1
mol/L LiClO 4-PC solution as the electrolyte. CV test was carried out with the voltage rang-
extending the evaporation time to 2 h for comparing their electrochromic properties, but
ingother
the from evaporation
−0.8 V to +0.8parameters
V at a scanwere
rate of 100the
kept mV/s.
same,Thebut
CAusing
test was conducted
ordinary at −0.8 V
WO3 powder
(coloring) and +0.8 V (bleaching) for 20 s. Optical transmittance spectra
as an evaporation source. The deposition rate of the nanostructured WO3 film was faster of WO 3 films at

colored state
originating fromanditsbleached state surface
large specific were examined at wavelength
area. It should ranging
be noted that fromdeposition
different 200 to 800
nm using
rates would aninevitably
ultraviolet/visible (UV/VIS)
cause different spectrophotometer
microstructures (Shimadzu
of the deposited UV-2550,
film. Tokyo,
However, for
Japan). The adhesion between WO 3 films and ITO substrates was examined by using
comparing their electrochromic properties, the thickness of the two WO3 films should be
ScotchTM adhesive tape (3M, St. Paul, MN, USA) with the adhesion force of 4.7 N/cm.

3. Results and Discussion

3.1. Morphology and Structure
Coatings 2021, 11, 959 3 of 10

the same, because the optical modulation rate, the memory effect, the adhesion and the
cyclic stability all greatly depend on the thickness of the electrochromic film.

2.2. Characterization
Morphology of two kinds of WO3 powder and two kinds of WO3 films was observed
by scanning electron microscopy (SEM) using a Sigma 500 instrument (Zeiss, Oberkochen,
Germany). The structure was examined by X-ray diffraction (XRD) analysis using a Cu Ka
radiation (Philips X’Pert diffractometer, Amsterdam, The Netherland). X-ray photoelectron
spectroscopy (XPS) analysis was performed by using a Thermo Fisher Scientific ESCALAB
250 XPS system, Waltham, MA, USA. The cyclic stability of WO3 film was measured by
cyclic voltammetry (CV) and the response time was tested by electrochemical double
potential step chronograph current test (CA) on an electrochemical workstation (CHI760E).
A three-electrode system was formed using WO3 film as the working electrode, Ag/AgCl
as the reference electrode, metal Pt plate as the counter electrode, and 1 mol/L LiClO4 -PC
solution as the electrolyte. CV test was carried out with the voltage ranging from −0.8 V
to +0.8 V at a scan rate of 100 mV/s. The CA test was conducted at −0.8 V (coloring)
and +0.8 V (bleaching) for 20 s. Optical transmittance spectra of WO3 films at colored
state and bleached state were examined at wavelength ranging from 200 to 800 nm using
an ultraviolet/visible (UV/VIS) spectrophotometer (Shimadzu UV-2550, Tokyo, Japan).
The adhesion between WO3 films and ITO substrates was examined by using ScotchTM
adhesive tape (3M, St. Paul, MN, USA) with the adhesion force of 4.7 N/cm.

3. Results and Discussion

3.1. Morphology and Structure
The morphology of both the nanostructured WO3 powder prepared by the chemical
method and the ordinary commercially-bought WO3 powder was analyzed in detail by
SEM as shown in Figure 2. The as-prepared nanostructured WO3 powder before annealing
showed the shape of nanosheets (Figure 2ai). Its size and distribution were uniform. The
WO3 nanosheets were cross-aggregated to form clusters. After annealing at 500 ◦ C, the
WO3 powder still showed uniformly nanoclusters (Figure 2aii). For comparison, the ordi-
nary WO3 powder showed a disordered state, among which some clusters were huge and
some were tiny (Figure 2b). XRD was employed to analyze the crystal structure and phase
properties of the two above WO3 powder. As can be seen in Figure 3a, both the nanostruc-
tured WO3 powder (Figure 3ai) and ordinary WO3 powder (Figure 3aii) were monoclinic
and had the three main diffraction peaks at 23.1◦ , 23.6◦ and 24.4◦ , suggesting that these two
kinds of WO3 powder had the same crystalline structure. However, the nanostructured
WO3 powders showed a bulging peak at 15–23◦ , suggesting that an amorphous component
existed, which demonstrated that the coexistence of crystalline phase and amorphous
phase was obtained. Furthermore, the high resolution XPS pattern of element W both in
the nanostructured WO3 powder after annealing and ordinary WO3 powder were depicted
in Figure 3b, which were the same. The peak energies of 35.3 and 37.5 eV were attributed
to W4f7/2 and W4f5/2 , respectively, which corresponded to tungsten atoms in a W6+ formal
oxidation state.
Two kinds of WO3 films were prepared by vacuum thermal evaporation respectively
using the annealed nanostructured powder and the ordinary powder. It can be seen that the
nanostructured WO3 film was composed of uniform nano-sheets, and there was no crack
on the surface, as shown in Figure 4a. While the ordinary WO3 film was composed of loose
agglomerated clusters, the surface cracked seriously, as illustrated in Figure 4b. Besides
the evaporation source, deposition conditions would also be responsible for the different
microstructures of the two WO3 films, which were tried to keep the same except the
evaporation time. Faster deposition rate of the nanostructured WO3 film originating from
its large specific surface area would cause different grain sizes and different morphologies.
As can be seen in Figure 5a, XRD spectra of the two WO3 films on the ITO glass substrates
showed that except for the diffraction peaks corresponding to the ITO substrate, there were
Coatings 2021, 11, 959 4 of 10

Coatings 2021, 11, x FOR PEER REVIEW 4 of 10

no other
Coatings 2021, 11, x FOR PEER REVIEW obvious diffraction peaks. Both of them were amorphous, mainly because 4 of 10 the
substrate temperature was not high enough during the evaporation process. As depicted
in Figure 5b, 6+ spin-orbit doublets existed in the XPS spectra of the W4f core level,
attributed to only Wand
W4f7/2 W4f5/2, respectively, which corresponded to tungsten atoms in a
proving
W theoxidation
6+ formal two films state.
were both WO3 .
attributed to W4f7/2 and W4f5/2, respectively, which corresponded to tungsten atoms in a
W6+ formal oxidation state.

Figure
Figure 2.
2. SEM
SEM images
SEMimages ofof
imagesof the
the WO
WO
the powder.
3 3powder.
WO (ai)
(ai) nanostructured
nanostructured WO WO 3 powder
3 powder before
before annealing,
annealing, (aii) (aii)
Figure 2. 3 powder. (ai) nanostructured WO 3 powder before annealing,
nanostructured
nanostructured WO
WO powder
33 powder after
after annealing.
annealing. (b)
(b) ordinary
ordinary WO WO 3 powder.
3 powder.
(aii) nanostructured WO3 powder after annealing. (b) ordinary WO3 powder.

Figure
Figure 3. 3.
XRDXRDand
andXPS
XPSspectra
spectraof
ofthe
theWOWO33 powder. (ai)
(ai) XRD
XRDspectrum
spectrumofofnanostructured
nanostructuredWO
WO3 powder
3 powderafter annealing,
after annealing,
(aii)
(aii)
Figure XRD
XRD spectrum
3. spectrum
XRD and ofofordinary
XPS ordinary WO
spectraWO 3 powder, (bi) XPS spectrum of nanostructured WO3 powder after annealing, (bii) XPS
of the powder,
WO 3 (bi) XPS
powder. spectrum
(ai) XRD of nanostructured
spectrum of WO powder
nanostructured WO 3after annealing,
powder after (bii) XPS
annealing,
3 3
spectrum of ordinary WO3 powder.
(aii) XRD of
spectrum spectrum
ordinaryofWO
ordinary
3 WO
powder. 3 powder, (bi) XPS spectrum of nanostructured WO 3 powder after annealing, (bii) XPS
spectrum of ordinary WO3 powder.
Two kinds of WO3 films were prepared by vacuum thermal evaporation respectively
using the annealed nanostructured powder and the ordinary powder. It can be seen that
Two kinds of WO3 films were prepared by vacuum thermal evaporation respectively
using the annealed nanostructured powder and the ordinary powder. It can be seen that
 from
from its
its large
large specific
specific surface
surface area
area would
would cause
cause different
different grain
grain sizes
sizes and
and different
different mor-
mor-
phologies.
phologies. AsAs can
can be
be seen
seen in
in Figure
Figure 5a,
5a, XRD
XRD spectra
spectra of
of the
the two WO33 films
two WO films on
on the
the ITO
ITO glass
glass
substrates
substrates showed
showed that
that except
except for
for the
the diffraction
diffraction peaks
peaks corresponding
corresponding to to the
the ITO
ITO substrate,
substrate,
there
there were
were no no other
other obvious
obvious diffraction
diffraction peaks.
peaks. Both
Both ofof them
them were
were amorphous,
amorphous, mainly
mainly be-be-
cause
cause the
the substrate
substrate temperature
temperature was was not
not high
high enough
enough during
during the
the evaporation
evaporation process.
process. AsAs
Coatings 2021, 11, 959 5 of 10
depicted
depicted inin Figure
Figure 5b,
5b, only
only WW6+6+ spin-orbit
spin-orbit doublets
doublets existed
existed in
in the
the XPS
XPS spectra
spectra ofof the
the W4f
W4f
core
core level,
level, proving
proving the
the two
two films
films were
were both
both WO
WO33..

Figure 4.SEM
Figure4.
Figure 4. SEMimages
imagesof
ofthe
of theWO
the WO
WO333 films.
films. (a) nanostructured WO
(a) nanostructured film,
WO33 film,
film, (b)
(b) ordinary
ordinary WO film.
WO333 film.
film.

Figure
Figure 5.
Figure 5. XRD
5. XRD andand XPS
XPS spectra
spectra of
spectra of nanostructured
of nanostructured WO
nanostructured WO
WO333 film
film and
film and ordinary
and ordinary WO
ordinary WO333 film.
WO film. (ai)
(ai) XRD
XRD spectrum
spectrum ofof nanostructured
nanostructured
nanostructured
WO3 film, (aii) XRD spectra of ordinary WO3 film, (bi) XPS spectrum of nanostructured WO3 film, (bii) XPS
WO
WO 33 film,
film, (aii)
(aii) XRD
XRD spectra
spectra of
of ordinary
ordinary WO
WO 33 film,
film, (bi)
(bi) XPS
XPS spectrum
spectrum of
of nanostructured
nanostructured WO
WO 33 film,
film, (bii)
(bii) XPS spectrum
XPS spectrum of
spectrum of
of
ordinary
ordinary WO
WO
ordinary WO film.33 film.
film.
3

3.2. Electrochromic Properties

Response time of the WO3 film was recorded by the current-time curve, as shown in
Figure 6. The response time was usually taken as 90% of the current change value. The
coloring time (t1 ) and the bleaching time (t2 ) of the nanostructured WO3 film were 8.40 and
1.39 s, respectively, while those of the ordinary WO3 film were 9.27 and 3.82 s, respectively.
 3.2. Electrochromic Properties
Response time of the WO3 film was recorded by the current-time curve, as shown in
Figure 6. The response time was usually taken as 90% of the current change value. The
coloring time (t1) and the bleaching time (t2) of the nanostructured WO3 film were 8.40 and
Coatings 2021, 11, 959 1.39 s, respectively, while those of the ordinary WO3 film were 9.27 and 3.82 s, respec-6 of 10
tively.

Figure 6. Response time of nanostructured WO3 film and ordinary WO3 film.
Figure 6. Response time of nanostructured WO3 film and ordinary WO3 film.
CV tests were carried out to record Li+ insertion/ extraction processes of the two
WOCV tests were carried out to record Li+ insertion/ extraction processes of the two WO3
3 films, as shown in Figure 7a. The results showed that the area enclosed by the CV
films,
curveasofshown in Figure
the ordinary WO 7a. The results showed that the area enclosed by the CV curve
3 film shrunk rapidly during long-term cycling (Figure 7aii).
ofAfter
the ordinary WO 3 film shrunk rapidly during long-term cycling (Figure 7aii). After 1000
1000 cycles, the ion capacity of the ordinary WO3 film decreased rapidly from 5.69
cycles,
to 1.08the mCion ·cmcapacity
−2 and the of decreasing
the ordinary rate WOwas 3 film decreased rapidly from 5.69 to 1.08
as high as 81%, indicating that its cycling
mC∙cm −2 and the decreasing rate was as high as 81%, indicating that its cycling stability
stability was poor. However, the CV curve of the nanostructured WO3 film changed less
was poor.7ai),
(Figure However,
and thethe ionCV curve decreased
capacity of the nanostructured
from 6.08 to WO 2.813 mCfilm·cm
changed
−2 afterless
1000(Figure
cycles,
7ai),
whichandwas the 53%
ion capacity
lower than decreased
that of from 6.08cycle.
the first to 2.81 mC∙cm the
Therefore, −2 after 1000 cycles, which
nanostructured WO3was film
53% lowerbetter
showed than cycling
that of stability
the first thancycle.theTherefore,
ordinary WO the nanostructured
3 film. The opticalWO 3 film showed
modulation rates
better cycling stability
at wavelength of 550 and than633thenm ordinary
(∆T550nm WOand ∆TThe
3 film.
633nm optical
) weremodulation
obtained byrates at wave-
comparing the
length of 550 and 633 nm (∆T and ∆T ) were obtained
transmittances of the two WO3 films in a fully colored state and a fully-bleached state. The
550nm 633nm by comparing the transmit-
tances
resultsofwere
the two WO3 films
represented in in a fully
Figure 7b.colored
The film state
wasand a fully-bleached
colored or bleached state.
at theThe resultsof
potential
were represented
3 V for 2 min. The in optical
Figure 7b. The film was
modulation ratescolored or bleached at the
of the nanostructured WO potential of 343.44%
3 film were V for
2 at
min.
550Thenm optical
and 55.92% modulation
at 633 nm rates of the7bi).
(Figure nanostructured
However, the WOoptical
3 film were 43.44% rates
modulation at 550of
nmtheand 55.92%WO
ordinary at 633
3 filmnmwere (Figure only7bi). However,
28.64% at 550thenmoptical modulation
and 40.68% at 633rates of the ordi-
nm (Figure 7bii).
nary
It wasWO 3 film were
known that the only ∆T28.64%
550nm at
and ∆T
550 nm
633nm andof 40.68%
the at 633
nanostructured nm (Figure
WO 3 7bii).
film It
were was
14%
known
higherthat thanthe ∆Tof
that theand
550nm ∆T633nmWO
ordinary of the nanostructured
3 film. As to the memory WO3 film were
effect, 14% higher of
transmittance than
the
nanostructured
that of the ordinary WOWO 3 film at 633
3 film. Asnm increased
to the memory byeffect,
21.14%transmittance
after being fully-colored for 8 h
of the nanostruc-
(Figure
tured WO 7ci),
3 filmwhile
at 633thatnm of the ordinary
increased byWO 3 film
21.14% increased
after being by 33.68% (Figure
fully-colored for 87cii), which
h (Figure
waswhile
7ci), close to thattheoftransmittance
the ordinary of WO the3 film
bleached state. by
increased Hence,
33.68% the (Figure
nanostructured WO3was
7cii), which film
showed
close to thea better memory effect.
transmittance of the bleached state. Hence, the nanostructured WO3 film
showed The adhesion
a better memory between effect.the two WO3 films and the ITO glass substrate was tested by
adhesive tape method and the testing process could be divided into three steps. First, the
transmittance of the WO3 film at 550 nm in initial state (T0 ) was measured by UV/VIS
spectrophotometer. Second, the ScotchTM adhesive tape at the force of 4.7 N/cm was
leveled and tightly attached to the surface of the WO3 film. Then the tape was torn up
and the transmittance of the WO3 film at 550 nm was measured again (Tn ). Finally, the
adhesion factor f was calculated according to the equation f = 1 − (Tn − T0 )/(100 − T0 ).
The closer the value of f was to 1, the greater the adhesion of the WO3 film was. Because
at this time almost no film was attached to the adhesive tape. On the contrary, the closer
the value of f got to 0, the worse the adhesion of the WO3 film was. At this moment, the
whole film was almost adhered to the adhesive tape. The calculated adhesion factor f was
shown in Figure 8. It was observed that the adhesion factor f of the nanostructured WO3
film was 0.99702, while that of the ordinary WO3 film was only 0.57148. Consequently, the
nanostructured WO3 film with greater adhesion was more reliable in practical applications,
Coatings 2021, 11, 959 7 of 10

Coatings 2021, 11, x FOR PEER REVIEW 7 of 10

which provided a potential solution for the adhesion problem in chemical fabrication of
films.

Figure7.7.Comparison
Figure Comparisonof ofthe
theelectrochromic
electrochromicproperties
propertiesofofthe thenanostructured
nanostructuredWO WO33film
film(i)
(i)and
andthe
theordinary
ordinaryWO
WO33 film
film (ii).
(ii).
(a)the
(a) thecyclic
cyclicstability,
stability,(b)
(b)the
theoptical
opticalmodulation
modulationrates,
rates,(c)(c)the
thememory
memoryeffect.
effect.

The adhesion between the two WO3 films and the ITO glass substrate was tested by
adhesive tape method and the testing process could be divided into three steps. First, the
transmittance of the WO3 film at 550 nm in initial state (T0) was measured by UV/VIS
spectrophotometer. Second, the ScotchTM adhesive tape at the force of 4.7 N/cm was lev-
eled and tightly attached to the surface of the WO3 film. Then the tape was torn up and
the transmittance of the WO3 film at 550 nm was measured again (Tn). Finally, the adhe-
sion factor f was calculated according to the equation f = 1 − (Tn − T0)/(100 − T0). The closer
the value of f was to 1, the greater the adhesion of the WO3 film was. Because at this time
almost no film was attached to the adhesive tape. On the contrary, the closer the value of
f got to 0, the worse the adhesion of the WO3 film was. At this moment, the whole film
was almost adhered to the adhesive tape. The calculated adhesion factor f was shown in
Figure 8. It was observed that the adhesion factor f of the nanostructured WO3 film was
 0.99702, while that of the ordinary WO3 film was only 0.57148. Consequently, the
nanostructured WO3 film with greater adhesion was more reliable in practical applica-
Coatings 2021, 11, 959 8 of 10
tions, which provided a potential solution for the adhesion problem in chemical fabrica-
tion of films.

Figure 8. Adhesion
Figure 8. Adhesion of
of the
the nanostructured
nanostructured WO film and
WO33 film and the
the ordinary
ordinary WO film.
WO33 film.

Electrochromic properties of the two WO3 films were summarized in Table 1. Faster
Electrochromic properties of the two WO3 films were summarized in Table 1. Faster
response time of the nanostructured WO3 film originated from its nano-blade morphology
response time of the nanostructured WO3 film originated from its nano-blade morphology
(seen in Figure 4a), which reduced the accumulation and accelerated the ion diffusion rate
(seen in Figure 4a), which reduced the accumulation and accelerated the ion diffusion rate
of Li++ [27]. The surface of the nanostructured WO3 film was smooth and uniform, which
of Li [27]. The surface of the nanostructured WO3 film was smooth and uniform, which
was conducive to improving the cycling stability. What is more, the nanostructured WO3
was conducive to improving the cycling stability. What is more, the nanostructured WO3
film had excellent adhesion with the ITO substrate because of its uniform and continuous
film had excellent adhesion with the ITO substrate because of its uniform and continuous
structure, while poor adhesion of the ordinary WO3 film probably originated from the
structure,morphology
cracking while poor adhesion
(Figure 4b).of These
the ordinary
results WO 3 film probably originated from the
indicate that a combination of chemical
cracking morphology (Figure 4b). These results indicate
and physical methods is effective in improving the properties thatofa electrochromic
combination offilms.
chemical
The
and physical methods is effective in improving the properties of electrochromic
above findings were verified several times and they showed good reproducibility. However, films. The
above findings were verified several times and they showed good reproducibility.
it should be mentioned that the electrochromic properties of the prepared nanostructured How-
ever, it
WO should be mentioned that the electrochromic properties of the prepared nanostruc-
3 films were not outstanding when compared with those recently reported, such as
tured WO
the optical3 films were not
modulation ofoutstanding when compared
the nanocolumnar structuredwith
WO those recently reported, such
3 film reaching 65% at the
as the optical modulation of the nanocolumnar structured WO 3 film reaching 65% at the
wavelength of 600 nm [18]. In Quy’s work, the response times of the PVE-WO3 film
wavelength
reached of 600
2.9 and 2.1 s,nm [18]. In Quy’s
respectively, work,
for the the and
coloring response timesprocess
bleaching of the[19].
PVE-WO3 film
reached 2.9 and 2.1 s, respectively, for the coloring and bleaching process [19].
Table 1. Comparison between the nanostructured WO3 film and the ordinary WO3 film.
Table 1. Comparison between the nanostructured WO3 film and the ordinary WO3 film.
Electrochromic Properties Nanostructured WO3 Film Ordinary WO3 Film
Electrochromic Properties Nanostructured WO3 Film Ordinary WO3 Film
response time
8.40 s/1.39 s 9.27 s/3.82 s
(coloring response time time)
time/bleaching 8.40 s/1.39 s 9.27 s/3.82 s
(coloring time/bleaching time)
cycling stability
cycling stabilityrate) 53% 81%
(ion capacity decreasing 53% 81%
(ion capacity decreasing rate)
optical modulation rates
optical modulation 43.44%/55.92% 28.64%/40.68%
(∆T550nm and ∆T633nmrates)
43.44%/55.92% 28.64%/40.68%
(∆T 550nm and ∆T633nm)
memory effect
memory effect rate) 21.14% 33.68%
(transmittance increasing
21.14% 33.68%
(transmittance increasing rate)
adhesion
0.99702 0.57148
(value of adhesion
adhesion factor)
0.99702 0.57148
(value of adhesion factor)
4. Conclusions
4. Conclusions
In this study, nanostructured WO3 films were prepared by the two-step method.
First In this study, nanostructured
nanostructured WO3 powderWO was3 films were prepared
chemically by the
synthesized, andtwo-step method. First
then nanostructured
nanostructured
WO 3 films were WO powder
prepared
3 bywas chemically
vacuum synthesized,
evaporation usingand
thethen nanostructured
nanostructured WO3
powder
as thewere
films evaporation
prepared source. With continuous
by vacuum evaporationand uniform
using nano-blade morphology,
the nanostructured powder as thethe
nanostructured
evaporation source. WO3 film showed
With better electrochromic
continuous and uniform properties than that
nano-blade of the ordinary
morphology, the
WO 3 film with better
nanostructured WO3 film cycling stability
showed and
better memory effect,
electrochromic strongerthan
properties adhesion
that oftothe
theordi-
ITO
substrate,
nary WO3afilm 14%with
higher modulation
better rate and and
cycling stability a faster response
memory time.
effect, Our research
stronger adhesionprovides
to the
an idea for preparing films with better properties by combination of different chemical and
physical methods.

Author Contributions: X.L. performed the experiments and wrote the paper. Z.L., W.H. and H.C.
helped with the experiments. X.T., Y.C. (Yeqing Chen) and Y.C. (Yu Chen) provided guidance and
Coatings 2021, 11, 959 9 of 10

helped in manuscript preparation. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by the National Natural Science Foundation (Nos. 51802229
and 12004285), Natural Science Foundation of Guangdong Province (Nos. 2018A030313561 and
2021A1515011935), Guangdong Basis and Applied Fundamental Research Fund (Nos. 2019A1515111190
and 2019A1515110778), Strong School Engineering Fund of Guangdong Province (No. 2020ZDZX2022)
and Science Foundation for Young Teachers of Wuyi University (No. 2018td04), Cooperative educa-
tion platform of Guangdong Province (No. [2016]31), Science and Technology Projects of Jiangmen
(Nos. [2017]307 and [2017]149), and Key Laboratory of Optoelectronic materials and Applications in
Guangdong Higher Education (No. 2017KSYS011).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The major work was carried out at the School of Applied Physics and Materials
and Research Center of Flexible Sensing Materials and Devices in Wuyi University.
Conflicts of Interest: The authors declare no conflict of interest.

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